Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1612—Non-macromolecular compounds
  • C09D5/1625—Non-macromolecular compounds organic
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/04—Disinfection
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/20—Prevention of biofouling

Definitions

• the present invention relates to combinations of 4-bromo-2-(4-chloro-phenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof, and a biocidal compound which provide an improved protecting effect against fouling organisms.
• compositions comprising a combination of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof, together with one or more biocidal compounds selected from (4-isopropylpyridinio)methyldiphenylboron, triphenylboron pyridine, benzalkonium chloride, capsaicine, clonidine, fenazaquin, glutaric dialdehyde, menadione sodium bisulfite, menadione piperazine bisulfite, menadione triaminetriazine bisulfite, menthol or a derivative thereof, N, N-bis(3-aminopropyl)dodecylamine, coco(fractionated)benzyldimethylammonium chloride, peracetic acid, pyridaben, tebufenpyrad, and zosteric acid
• component 1 4-bromo-2-(4-chloro-phenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (hereinafter referred to as component 1) and a biocidal compound selected from 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof, together with one or more biocidal compounds selected from (4-isopropylpyridinio)methyldiphenylboron, triphenylboron pyridine, benzalkonium chloride, capsaicine, clonidine, fenazaquin, glutaric dialdehyde, menadione sodium bisulfite, menadione piperazine bisulfite, menadione triaminetriazine bisulfite, menthol or a derivative thereof, N,N-bis(3-aminopropyl)dodecylamine
• EP-0,746,979 describes the use of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile in antifoulant compositions which are applied to underwater surfaces in order to prevent the attachment of fouling organisms to said underwater surfaces.
• WO-03/039256 discloses combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile with bethoxazin, DCO IT, tolylfluanid and dichlofluanid for protecting materials against fouling organisms.
• biocidal compounds referred to as components (II), are the following:
• menthol Derivatives of menthol are e.g. ( ⁇ )-menthol, ( ⁇ )-trans-p-menthan-3,8-diol, ( ⁇ )-menthyl chloride, 3-[[5-methyl-2-(l methylethyl)cyclohexylloxyl-1,2-propanediol (also known as menthol propylene glycol carbonate), ( ⁇ )-isopulegol), and ( ⁇ )-menthone, which have been described as antifouling agents in WO-01/95718.
• Another derivative is menthol propyleneglycol carbonate which has been described for its insect repellent activity in WO-2005/025313.
• component (I) is used throughout this text, it is meant to include said compound both in base or in salt form, the latter being obtained by reaction of the base form with an appropriate acid.
• Appropriate acids comprise, for example, inorganic acids, such as the hydrohalic acids, i.e.
• Said component (I) may also exist in the form of
• aquatic organisms such as algae, fungi, bacteria, microbes, and aquatic animals such as, e.g. tunicates, hydroids, bivalves, bryozoans, polychaete worms, sponges, barnacles, and molluscs.
• aquatic organisms such as algae, fungi, bacteria, microbes, and aquatic animals
• tunicates e.g. tunicates, hydroids, bivalves, bryozoans, polychaete worms, sponges, barnacles, and molluscs.
• the attachment or settlement of said organisms is also known as ‘fouling’ of a structure.
• the exterior, but possibly also the interior of the object may deteriorate, the surface changes, e.g.
• the common method of controlling the attachment of fouling organisms is by coating the structure to be protected with a composition which comprises an antifouling agent.
• the combinations as claimed in the present invention are especially suitable to protect surfaces or objects in constant or frequent contact with water from fouling or attachment or settlement of algae, by applying to said surfaces or objects a composition comprising component (I) and one of the components (II) in respective proportions to provide a synergistic effect against fouling organisms.
• Examples of said surfaces or objects are for instance, shiphulls, harbor installations, piers and pilings, drying docks, sluice-gates, locks, mooring masts, buoys, offshore oil rigging equipment, drilling platforms, bridges, pipelines, fishing nets, cables, ballast water tanks, ship reservoirs that draw water from infested bodies of water, recreational equipment, such as surfboards, jet skis, and water skis, and any other object in constant or frequent contact with water.
• the invention also provides a method to protect materials, in particular surfaces or objects in frequent or constant contact with water, against fouling organisms by applying to said objects a composition comprising an effective antifouling amount of a combination of component (I) together with one of the components (II) wherein the amount of component (I) and component (II) are in respective proportions to provide a synergistic effect against fouling organisms.
• An “antifouling effective amount” is that amount that will kill or inhibit the growth, reproduction or spread of a significant number of fouling organisms.
• the present invention further provides a method of protecting a surface which comprises applying to the surface a composition comprising an effective antifouling amount of a combination of component (I) together with one of the components (II) wherein the amount of component (I) and component (II) are in respective proportions to provide a synergistic effect against fouling organisms.
• An especially important use of the method of the invention comprises a method for inhibiting fouling of a ship's hull, which comprises applying to the hull an antifouling composition in accordance with the invention. Fouling on the hulls of ships for example increases frictional drag with a corresponding decrease in speed and maneuverability and an increase in fuel consumption and increased maintenance costs associated with removal of the fouling.
• compositions comprising a combination of component (I) together with one of the components (II) wherein the amount of component (I) and component (II) are in respective proportions to provide a synergistic effect against fouling organisms
• constructions such as, e.g. swimming pools, baths, cooling water circulation circuits and industrial baths in various installations, e.g. in manufacturing plants or in air-conditioning installations, the function of which can be impaired by the presence and/or the multiplication of fouling organisms.
• Further examples are buildings and parts of buildings such as floors, outer and inner walls or ceilings, or places suffering from dampness such as cellars, bathrooms, kitchens, washing houses and the like, and which are hot-beds for fouling. Fouling not only is problematic from the viewpoint of hygiene and aesthetics, but also causes economic losses because said buildings and/or decorating materials deteriorate more rapidly than desired.
• ballast water is treated or disinfection of ballast water to reduce or eliminate the presence of aquatic organisms such as phytoplankton (dinoflagellates and diatoms), crustaceans (crabs, shrimp, copepods, amphipods), rotifers, polychaetes, mollusks, fish, echinoderms, ctenophores, and coelenterates.
• aquatic organisms such as phytoplankton (dinoflagellates and diatoms), crustaceans (crabs, shrimp, copepods, amphipods), rotifers, polychaetes, mollusks, fish, echinoderms, ctenophores, and coelenterates.
• synergistic antifouling compositions of the present invention can also be used in a variety of applications:
• Fouling organisms is meant to comprise organisms that attach, settle, grow on or adhere to various kinds of surfaces, in particular in humid or aqueous environments such as, marine waters, fresh waters, brackish waters, rain water, and also cooling water, drainage water, waste water and sewage.
• Fouling organisms are Algae such as, for example, Microalgae, e.g. Amphora, Achnanthes, Navicula, Amphiprora, Melosira, Cocconeis, Chlamydomonas, Chlorella, Ulothrix, Anabaena, Phaeodactylum, Porphyridium ; Macroalgae, e.g.
• the relative proportions of component (I) and one of the components (II) in compositions comprising a combination of component (I) and one of the components (II) are those proportions which result in a synergistic effect against fouling organisms when compared to a composition including, as an active ingredient, either component (I) alone or a component (II) alone.
• the said synergistic effect may be obtained within various proportions of components (I) and (II) in the composition, depending on the kind of fouling organism towards which effect is measured and the substrate to be treated. Based on the teachings of the present application, determination of the synergistic effect of such combinations can be performed according to the procedures of the Poison Plate Assay as described in Experiment 1.
• the suitable proportions by weight of the amount of component (I) to component (II) in the combinations should lie in the range from 10:1 to 1:10. Particularly, this range is from 8:2 to 2:8, more particularly from 3:1 to 1:3 or 2:1 to 1:2.
• Another particular ratio of component (I) to component (II) in the compositions of the present invention is a 1:1 ratio between component (I) and one of the components (II).
• the quantity of each of the active ingredients in compositions comprising a combination of component (I) and one of the components (II) will be so that a synergistic effect is obtained.
• the ready to use compositions of the present invention comprise component (I) in an amount of at least 1 wt % based on the total weight of the composition.
• such ready to use compositions comprise component (I) in an amount from 1 wt % to 40 wt %, or more particular from 3 wt % to 30 wt %, based on the total weight of the composition.
• the amount of component (II) in said ready to use compositions will be so that a synergistic antifouling effect is obtained.
• the amount of component (II) may range from 1 wt % to 30 wt %, more particular from 2 wt % to 20 wt % based on the total weight of the dry mass of the composition.
• the antifouling compositions to be used directly can be obtained from concentrates, such as e.g. emulsifiable concentrates, suspension concentrates, or soluble concentrates, upon dilution with aqueous or organic media, such concentrates being intended to be covered by the term composition as used in the definitions of the present invention.
• Concentrates used in the form of a paint composition can be diluted to a ready to use mixture in a spray tank shortly before use.
• a composition comprising a combination of component (I) and one of the components (II) in respective proportions to provide a synergistic effect against fouling organisms is thus suitably used together with carriers and additives, including wetting agents, dispersing agents, stickers, adhesives, emulsifying agents and the like such as those conventionally employed by the artisan in preparing antifouling compositions.
• the antifouling compositions of the present invention may further comprise suitable substances known in the art of formulation, such as, for example natural or regenerated mineral substances, solvents, dispersants, surfactants, wetting agents, adhesives, thickeners, binders, anti-freeze agents, repellents, colour additives, corrosion inhibitors, water-repelling agents, siccatives, UV-stabilizers and other active ingredients.
• suitable surfactants are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
• surfactants will also be understood as comprising mixtures of surfactants.
• Appropriate carriers for liquid formulations are any liquid that does not adversely affect the active ingredients, for example, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, glycerin, etc.), ketones (for example, acetone, methyl ethyl ketone, etc.), ethers (for example, dioxane, tetrahydrofuran, cellosolve, diethylene glycol dimethyl ether, etc.), aliphatic hydrocarbons (for example, hexane, kerosene, etc.), aromatic hydrocarbons (for example, benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc.), halogenated hydrocarbons (for example, chloroform, carbon tetrachloride, etc.), acid amides (for example, dimethyl formadide, etc.), esters (for example, methyl a
• Emulsifiable concentrates usually contain, in addition to the organic solvent(s), from about 10 to 50% by weight of the combination of active ingredients, from about 2 to 20% of emulsifying agent(s) and up to 20% other additives such as stabilisers, corrosion inhibitors and the like.
• the combination of components (I) and (II) may also be formulated as a suspension concentrate, which is a stable suspension of the active ingredients in a (preferably organic) liquid intended to be diluted with water before use.
• a suspending agent selected from known protective colloids and thixotropic agents.
• Concentrations used for fenazaquin, and glutaric dialdehyde concentration of total single active ingredient in the toxicity tests—a series of concentrations increasing with steps of 1/3: 0.03-0.04-0.05-0.06-0.08-0.11-0.15-0.20-0.27-0.35-0.47-0.63-0.84-1.13-1.50-2.00-2.67-3.56-4.75-6.33-8.44-11.25-15.00-20.00-26.70-35.60-47.46-63.28-84.38-112.50-150.00-200.00 ppm.
• Synergism between component (I) and one of the components (II) was determined by a commonly used and accepted method described by Kull F. C. et al. in Applied Microbiology, 9, 538-541 (1961) using the Synergy Index, which is calculated as follows for two compounds A and B:
• MIC is the minimum inhibitory concentration, i.e. the lowest concentration of each test compound or mixture of test compounds sufficient to inhibit visible growth.
• Synergy Index When the Synergy Index is greater than 1.0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1.0, synergism is demonstrated.
• Synergy Index When the Synergy Index is greater than 1.0, antagonism is indicated. When the SI is equal to 1.0, additivity is indicated. When the SI is less than 1.0, synergism is demonstrated.

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• 2007
  • 2007-04-10 CN CN2007800127547A patent/CN101420851B/zh active Active
  • 2007-04-10 WO PCT/EP2007/053449 patent/WO2007116051A1/en active Application Filing
  • 2007-04-10 AU AU2007235922A patent/AU2007235922B2/en not_active Ceased
  • 2007-04-10 CA CA002647444A patent/CA2647444A1/en not_active Abandoned
  • 2007-04-10 US US12/296,353 patent/US20090093443A1/en not_active Abandoned
  • 2007-04-10 BR BRPI0711535-0A patent/BRPI0711535A2/pt not_active IP Right Cessation
  • 2007-04-10 JP JP2009504716A patent/JP5119238B2/ja active Active
  • 2007-04-10 NZ NZ571654A patent/NZ571654A/en not_active IP Right Cessation
  • 2007-04-10 EP EP07727917A patent/EP2009991A1/en not_active Withdrawn
  • 2007-04-10 RU RU2008144198/21A patent/RU2426313C2/ru not_active IP Right Cessation
  • 2007-04-10 MY MYPI20084001A patent/MY145557A/en unknown
• 2008
  • 2008-11-04 KR KR1020087026989A patent/KR101342901B1/ko active IP Right Grant
  • 2008-11-04 NO NO20084639A patent/NO20084639L/no not_active Application Discontinuation
• 2009
  • 2009-07-28 HK HK09106941.8A patent/HK1128860A1/xx unknown

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